Process for printing acetate artificial silk



Patented Feb. 4, 1936 UNITED STATES NT OFFICE PROCESS FOR PRINTING ACETATE ARTIFICIAL SILK Basel, Switzerland No Drawing. Application (October 15, 1934, Serial No. 748,424. In Switzerland October 21, 1933 12 Claims.

This invention relates to a process of printing acetate artificial silk fast tints by means of dyestuffs containing metals in complex union.

As dyestufis containing metal in complex union 5 there may be used, for example, the metal compounds of dyestufis containing the groups which unite with metals and belong to the anthraquinone series, triarylmethane series or azo series and in the latter case monoor poly-azo dyestufls.

Dyestuffs of the anthraquinone series containing the groups which unite with metals are dyestufis containing two hydroxyl groups standing in ortho-position to each other, whereas the dyestuiis of the triarylmethane series containing the 15 groups which unite with metal binding groups possess the so-called salicylic acid grouping, i. e. such a grouping where a hydroxyl group is present in ortho-position to a carboxyl group. Dye stufis of the azo series containing the groups 20 which unite with metals are the ortho-hydroxy dyestuffs and the ortho-carboxy dyestuffs, as well as such dyestuffs which contain a carboxyl group in ortho-position to a hydroxyl-group. The metaliferous dyestuffs may contain either one 25 metal only, for example, chromium, copper, nickel, cobalt, titanium, vanadium, manganese or iron,

or they may contain several metals. Well suited for the purpose are the metal compounds of the azo-dyestufis, particularly of the ortho-hydroxy- 30 azo-dyestuiis, and of those which are sparingly soluble to insoluble in water, for instance, owing to the absence of sulfonic or carboxylic groups, give, in respect of fixation, fastness and yield, particularly good results, and which contain as metals manganese, iron, cobalt or nickel,

i. e. such metals whose atomic weights lie between 55 and 59.

For printing acetate artificial silk in a manner described by this invention it is particularly advantageous, especially in the case of dye-stuffs sparingly soluble to insoluble in water, to use the dyestufi in the form of a paste, for example, a paste obtained by grinding the filter-press cake or, in the form of a dry dyestuff preparation which contains the dyestufi in a particularly favourable form for the purpose of printing. These pastes or uble salt or an aliphatic-aromatic or hydro-aromatic-sulfonic or -carboxylic acid such as the alkali salts of benzene-sulfonic acid, dimethyl-sulianilic acid, phthalic acid, tetrahydronaphthalene-sulfonic acid, phenoxy-acetic acid or a sulfamide such as para-toluene sulfamide; and on the other hand a water soluble alcohol such as glycerine, ethyl alcohol, ethylene glycol, thio-diglycol, an oxidation product of thio-diglycol, or a condensation product of a polyhydric alcohol with 10 urea either alone or together with a hydrotropic agent.- Furthermore, the dyestuff paste or preparation may be made with the addition of a product of soapy nature such as ordinary soaps or sulfonated castor oil, for instance, Turkey red oil, as well as of metal compounds such as a compound of iron, copper or aluminium. All these additions may, in many cases, be incorporated with the printing paste instead of with the dyestufl.

The operation of printing the acetate artificial silk by this process is similar to that of printing acetate artificial silk by the usual processes.

The invention is illustrated by the following examples, the relationship between parts by weight and parts by volume being that which exists between the kilogram and the litre:

Example 1 A printing paste is prepared by dissolving cold 20 parts by weight of the nickeliferous dyestufl of the formula from diazotized 4-chloro-2-amino l-phenol and resorcinol in 230 parts by volume of alcohol mixed with 50 parts by volume of glycerine, then this solution is 'ntroduced into 700 parts of gum (1 1) Acetate artificial silk is printed with this printing paste, dried,steamed for one hour in a steam chest under /4 atmosphere pressure and washed; the print produced is a fast reddish-orange.

Example 2 A printing paste is prepared by stirring 20 parts of the manganiterous azo-dyestufi of the formula NO: from diazotized 4-nitro-2-amino-1-phenol and resorcinol at 60 C. with 230 parts by weight 01' water and adding 50 parts by volume of glycerine and 700 parts of gum (1:1).

Acetate artificial silk is printed with this paste, dried, steamed for one hour in a steam chest under $4 atmosphere pressure and washed and soaped at 60 C.; the print is a fast brown tone.

An olive-brown is produced by using the terruginous dyestufi from diazotized 4-chloro-2- amino-l-phenol and resorcinol, while the terruginous dyestuif from diazotized 4-chloro-2- amino-l-phenol and 2-hydroxynaphthalene yields, when printed on acetate artificial silk, a

fast brown.

Example 3 20 parts of a powder, obtained by grinding 40 parts of the nickeliferous dyestufi' from diazotized 4-chloro-2-amino-1-phenol and resorcinol with 60 parts of sulfite cellulose waste liquor in the form of a powder, or which may also be obtained by intimately grinding and evaporating 40 parts of the dyestufl with 120 parts of sulfite cellulose waste liquor free from lime, are made into a paste with 280 parts of luke-warm water and introduced into 700 parts of gum (1:1), while stirring.

Acetate artificial silk is printed with this printing color. After drying, steaming for to 1 hour, washing and soaping an acetate artificial silk printed a reddish orange shade is obtained.

The following table contains a series of dyestufls to be used according to the present process, and the shades obtainable therewith:

Dyestufl containing metal in complex union C of the No. printed acetate Dyastufl Metal artificial silk 1 on re-- Yellow.

N=N -C C 0 CN H 2 0H Mn Beddish yellow. N=N("3(|JCH;

HO-C

3 dn About 50% oi Yellow.

Zn about 50% of Cu 4 .do Fc Do. 5 do C0 D0. 6 d0 About $7 of Gold-or- Co about ange. m 01 Al. I do Ni Yellow.

Dyestnfi containing metal in complex union Metal a of N1.

About of Oo+mut of On.

About 30% o! Fe+nbout About 0! cr-i-i bzint 50% of Co.

About 50% of Cr+nbont 80% of Ni.

About 50% of Cr-l-about 50% of Fe.

About 00% o! AH-abont 40930! 00.

About 0! Ni-l-mut 60% of Cu.

About 33% 0! 0 C a ll.

Bluish red.

Bluieb red.

Brown.

Reddish violet.

Reddish brown.

Reddish violet.

Violet.

Beddish violet.

V olet.

Brown.

Red-violet.

Dyestufl containing metal in complex union Dyestuil containing metal in complex union 001, of

the the No. prlnud No. printed mutate acetate Dyestnfl Motal artificial Dyestm! Metal artificial silk silk 26 OH 011 About 60% of Orange 46 0H OK Or Gray,

9+ {gout o o. N=N N==N 27 .....do Go Red.

28 .'--.do About 50 7 of B e i g o .Cr+ab8ut (em).

29 "410 Ni Reddish 47 0H 0H Ni Orange.

orange.

N=N 30 .....d0 About 80% of Gold-or- Cr+abou mm. 20% of Cu. 011

31 -d0 About 60% of Raddish Al+about orange. 7

40% of Cu, 48 OH OH Fm.-. Olive.

32 do About 0! D0. N=N

o 01 A on 33 do About 507 of 0mm.

Ni+nbo ut 50% 01' Zn.

7 011 A1 Red. 34 OH 0!! Mn Yoilow.

N0 H 0 OH 35 (in Al Gold orange. 50 -....do Co Grey. 36 do About 60% 01' n o x a o 51 n Ni. Violet.

Co-l-about (Q0111). of Cu. 52 -...do About 50% 01' Grey,

Cr-l-about 37 do About 20% of Pink. 50% of 00.

N i+about 80% of Cu. 63 -..-.do About 21% of Red-via Fo+about lot. 33 do About30%o( Beige 20%0IA1 Fo+about (ecru). about a 70% 0! Ni. of Cu.

39 do About 50% of Orange. 64 M About-50% of Brown- Ni+about Co+about violot.

50% of Zn. 50% of Cu.

66 (in About 50% 0! Violet. 40 OH About 20% of Brown. Ni+about Ni+about 50% of Zn. 7 50% of Fo+ N=N about 30% 56 .do 01'. Grey.

H0 51 Abo a 507 1 n u o o on Cu+ab8u brown OINHI a of Zn.

, E0 41 .do About 60% of D0.

Fe-i-about g 0 MD- 42 h Fe. Do.

43 in Ni. Pink.

58 .....d0 Al Scarlet 44 do Mn. Onnp. red.

45 .-.-.do About% 0; Rod. so ---..ao Ni--- Do,

Ali-about v 50%08211. M Mn Do.

Ill]

Dycstufl containing metal in complex union C01. Dyostufl contoinlng metal in complex union Com 0' the the N0. Drlntcd No. pdntod lactate ncctato Dyastufl Maul lrtlflcial Dywtufl Metal u-tlflcinl Iilk silk 61 Co Reddlsh 76 Fe... Brown.

OH violet. 0H

O HO HaN 77 -do Mn Orange. 62 fin Ni B o r deaux. 78 do Cr. B e i go (com). 63 do Mn R e d brown. 79 OH Fe.. Reddish violet. 64 do About 0! Rod.

Mn-l-about No a of EN 65 OH Mn Yellow.

N=N- c :-om HOC\ /1 L R0 d0 Cr Gray.

N 81 COOH I Fe Brown.

82 Ni Violet- 0H brown. HIN N=N- l EN 67 --do About 50% 0f Reddish Co+about ormn. 50% of On.

83 .d0 AbOllt 56% 0f Gold-or- Fe+about ange. 68 do About 2)% ol Pmk. 50% of Sn Fc-l-about 50% of Al+ 84 (In Fc Do, about 30% 0! Cu. 85 do 00. Grey.

85 Ni. B l u e 69 do About 25% of Vlolot. 0H my Co+about 50% of Al+ NH- about 25% of Cu.

70 -do About 11% of Grey.

Co-l-nbou Cl 80% of F0.

37 1 dn 00-... Grey. 7 --.d0 About m of Brown.

Mn+nbout as do Cr. Do. 80% of Fe. I 80 on C0 D0. N.

a on 60% of Zn. No N-N H0 73 Or B o l I a 14 on Fo Pink.

N=N N on C0 Olive.

N N=N X 00011 75 .do (.r Guy.

Dyestufl containing metal in complex union 001m. Dyestufl containing metal in complex union C0101- oi the of the printed printed acetate acetate Dyestufl Metal artificial Dyestufl Metal artlficlal silk silk 91 OH Fe.......-.- Yellow, 99 HO OH CL. Greenblue.

HaN HO S 0:11

I H E E0 0 0 OH 100 (I) (')H Or- Violet. 92 Cr B l u i s h on violet. 0H

MIN 7 1 101 n; (in. Do.

03 on On. Olive.

NO N=N 102 I OH Cl'-- Grey.

BIN N=N NH 04 OK Or B o r- HO, S 2

deaux.

N=N N=N NH:

OH CL; Violet.

103 OOOH Cr Blue- N= green. N0 no NE: N=N

00 Or B l u e HO S NH:

\ KNOB. H0 0 O 97 Cr....-.-.-..- Reddlsh H0 8 NO,

blue.

104 COOH CL- Grey- OOOH 00H blue.

H0: NH: B

N: 98 HO (f 011 Cu............ Violet.

OH OH H consisting in printing acetate artificial silk with dyestufis containing metal in complex union which are sparingly soluble to insoluble in water.

2. Process for printing acetate artificial silk, consisting in printing acetate artificial silk with ortho-hydroxyazo-dyestufis containing metal in complex union which are sparingly soluble to insoluble in water.

3. Process for printing acetate artificial silk, consisting in printing acetate artificial silk with ortho-hydroxyazo-dyestufis containing metal of the atomic weight 55 to 59 in complex union, which dyestuffs are sparingly soluble to insoluble in water.

4. Process for printing acetate artificial silk, consisting in printing acetate artificial silk with ortho-hydroxyazo-dyestuffs containing metal of the atomic weight 55 to 59 in complex union and resorcinol as coupling component, which dyestufis are sparingly soluble to insoluble in water.

5. Process for printing acetate artificial silk, consisting imprinting acetate artificial silk with ortho-hydroxyazo-dyestufis of the formula OH on containing metal of the atomic weight 55 to 59 in complex union.

6. Process for printing acetate artificial silk,

consisting in printing acetate artificial silk with ortho-hydroxyazo-dyestufis of the formula tate artificial silk which has been printed with azo-dyestuffs containing metal in complex union which are sparingly soluble to insoluble in water.

8. A composition of matter, consisting of acetate artificial silk which has been printed with ortho-hydroxyazo-dyestufis containing. metal in complex union which are sparingly soluble to insoluble in water.

9. A composition of matter, consisting of acetate artificial silk which has been printed with ortho-hydroxyazo-dyestufis containing metal of the atomic weight 55 to 59 in complex union. which dyestufis are sparingly soluble to insoluble in water.

10. A composition of matter, consisting of acetate artificial silk which has been printed with ortho-hydroxyazo-dyestufis containing metal of the atomic weight 55 to 59 in complex union and resorcinol as coupling component, which dyestufis are sparingly soluble to insoluble in water.

11. A composition of matter, consisting of acetate artificial silk which has been printed with ortho-hydroxyazo-dyestufis of the formula on on N=N I containing metal of the atomic weight 55 to 59- in complex union.

12. A composition of matter, consisting of acetate artificial silk which has been printed with ortho-hydroxyazo-dyestufi's of the formula on on containing nickel in complex union.

WOLFGANG ARTHUR SCHURJCH. 

